Method of making varnishes having high paraffin hydrocarbon tolerance and the product thereof



Patented Nov. 21, 1939 UNITED STATES PATENT oer-ice MErnon or maxiizg vnmsnns HAVING HIGH PARAFFIN HYDROCARBON TOLEB! ANCE, AND PRODUCTTHEREOF" No Drawing.

Application December 2, 1937.

- Serial No. 177,826

. 16 Claims. This invention relates to a method of making a varnish froma paramn hydrocarbon-insoluble a paraflin hydrocarbon-insoluble resin,substantially free from rosin is recovered. For many years this productwas considered practically valueless commercially and was accordinglydiscarded.

It has been found, however, that among other uses, it is possible toformulate varnishes from this pine wood-derived paraffinhydrocarbon-insoluble resin, drying oils, such as, for example, linseedoil, China-wood oil, etc., driers and solvent thinners. In order toformulate such varnishes in the prior art, however, it has beennecessary to use special solvents, such as hydrogenated petroleumsolvents or aromatic hydrocarbon solvents to obtain the proper workingconsistency. It has been impossible heretofore especially with varnishesof less than 25-gallon oil length to thin the varnishes made from thisparamn hydrocarbon-insoluble pine wood resin to any substantial degreewith solvents composed as solely of volatile paraflin hydrocarbons. Now,I have found that I may prepare varnishes containing the aforesaidparaffin hydrocarbon-insoluble resin derived from pine wood,

' F. and held at that temperature for the proper body, determined inwaysweillrnown to those skilled in the art. The metal or combination ofmetals in suitable form, as more fully described below, are preferablyadded on the upheat at a temperature of approximately 500 F. When theproperties of the varnish are those desired for any particular purpose,heating is discontinued, the varnish allowed to-cool and reduced withvolatile diluents to the desired consistency at a temperature from about450 F..to about 475 F. It will be understood that.this lattertemperature range is in no way critical, because it is possible to thinat higher or lower temperatures depending upon the particular conditionsexisting.

' In order to obtain the best results, however,

. I have foundthat it is necessary to make some changes in the generalcooking procedure given above; The parafiin hydrocarbon-insoluble resinderived from pine wood is not soluble in vegetable or animal oils, withthe exception of castor oil, at ordinary temperatures. When heated to atemperature of about 565 F. to 600 F., however, the aforesaid resin andoils become miscible and can .be thinned'with aromatic hydrocarbons orhydrogenated petroleum solvents. Even with such thinners, however, thereis frequent precipitation of the resin from the varnish during storage.The undesirability of this is of course very apparent.

After considerable experimental work, a cooking procedure was developedwhich prevents any resin precipitation from the finished varnish soduring storage. This cooking procedure isessentially as follows: 100pounds of the paraffin hydrocarbon-insoluble resin derived from pinewood are placed in a varnish kettle and to this are added from about 2to about 7 gallons of as oil, preferably about 5 gallons of oil. Thismixture is then heated to a temperature of about 565 F. to about 600 F.,preferably from about 570 F. to about 575 F. and held at thattemperature until foaming subsides, which will usu- 40 l ally be fromabout 5 to 10 minutes. When certain metalsareadded to increase theparaihn hydrocarbon tolerance in accordance with my invention this willpreferably be done at the point above where the temperature has reachedabout 480 I". to about 500 F. After this initial cooking with onlypart'of the oil, which is the essential part of the new cookingprocedure, further quantities of' oil may then be added to, produce anyoil length desired and the whole then again heated to about 565 lit-600F., preferably to about 570 F.-575 F. and held there until the desiredbody is obtained. It is ,then' allowed to cool to a temperature,preferably, although not necessarily, of about 450 lib-475 F.

and thinned to the desired working consistency with petroleum diluents.

Among the paraflin hydrocarbon diluents, which I may use for thinning myvarnishes, are any of the petroleum diluents' commonly used in the art,known under various trade names,.

and familiar to those skilled in the art.

I have determined from a large number of varnishes prepared in thegeneral manner indicated above that the most suitable metals to use tosubstantially increase the volatile paraflin hydrocarbon tolerance of avarnish containing a paraffin hydrocarbon-insoluble resin derived frompine wood, are lead, manganese, cobalt,

' cooking procedure are of that class which promote drying ofunsaturated oils and, therefore, varnishes prepared as above will havedrying properties depending upon the particular metals introduced andthe amounts thereof. It is to be distinctly understood, however, thatthe incorporation of these metals during the cooking procedure isnot forthe purpose primarily of producing varnishes which have the desireddrying qualities but, .in accordance with my invention,

for the purpose of making varnishes, containing a paraffinhydrocarbon-insoluble resin derived from pine wood, which have asubstantially greater tolerance for parailin hydrocarbon type diluents.I have found, for example, that zinc and tin have little or no effect onthe drying of a varnish prepared from the above mentioned resin, yetfrom the standpoint of producing paramn hydrocarbon-tolerance thereof,they operate very satisfactorily. The customary procedure forintroducing these metals is in the form of various compounds thereofwhich have a substantial reactivity in the resin-oil mixtures at thetemperatures of cooking and thus make the metal available to perform itsfunction of increasing the paraflin hydrocarbon tolerance of a paraflinhydrocarbon-insoluble pine wood resin, drying oil, semi-drying orsynthetic drying oil varnish. These metals may be introduced in the formof suitable compounds thereof, among which are, for example, lead aslitharge, manganese as manganese dioxide, cobalt as cobalt resinate,zinc as zinc oxide or zinc acetate and tin as stannous chloride. It willbe understood that these salts are by way of example only and that I amnot limited to the use of these metals in the combinations above givenin practicing my invention.

On the basis of thinning a varnish to 50% nonvolatile content, 25 gallonoil length varnishes or higher can be thinned solely with paramnhydrocarbons, liquid at ordinary temperatures, without the addition ofany metals, using only the modified cooking procedure before given. Iflower non-volatile contents are necessary, however, it will be foundthat even these higher oil length varnishes must be cooked with themetals before mentioned. For varnishes with oil lengths from 12 gallonsto less than 25 gallons, thinning to 50% non-volatile cannot be donewith paraflln type hydrocarbons alone, unless the metals beforementioned are incorporated therein during the cooking procedure. Forvarnishes less than 12 gallons oil length, although the parafflnhydrocarbon tolerance is increased considerably by metal additions, itwill be found that some, aromatic hydrocarbon type solvents will benecessary,' if it isdesired to'thin the var-- nish to the usual workingconsistency.' The marked improvement in paraflln hydrocarbon toleranceis most apparent in the range from about 12 gallons to less than 25gallons oil length,

in which range it has not been possible hereto- 4 fore, to use onlypetroleum type thinners for di- Regardless of the oil length varnish,

lution. however, the addition of the metals before mentionedsubstantially increases the paraffin hydrocarbon tolerance of a varnishcontaining an oil of the groups above mentioned and a parafllnhydrocarbon-insoluble resin derived from pine wood.

The mechanism whereby these metals perform this function is unknown.That a resin which is substantially completely insoluble in paraffinhydrocarbons can be treated'by a simple cooking procedure in making avarnish which is compatible with such solvents is, as far as I am aware,a completely new and unexpected result.

I have found that the minimum quantity of metal as free metal, that is,not combined, on the basis of the oil present in the varnish, which isnecessary to produce this increased tolerance of the aforesaid resin-oilvarnish for paramn hydrocarbon diluents, is as follows:

Per cent 4 Lead, abo /2 Manganese, about 0.4 Cobalt, abo 0.6 Zinc, abo0.5 Tin, abo 0.5 A lead-manganese combination:

Lead, abo 1.0 Manganese 0.1 A lead-cobalt combination:

Lead, ahmif. 1.0 Cobalt, about 0.1

The maximum quantity of metal which may be incorporated is not a fixedamount but obviously will be limited in the practical adaptation of mylimited to the maximum quantity shown and may exceed this if aparticular substance indicates such a procedure. Here, as before, theamounts shown are on the basis of the oil present in the varnish.

From the standpoint of increasing the tolerance of my varnishes forvolatile paraflin hydrocarbons and simultaneously produce satisfactorydrying qualities, I have found that the lead-manganese composition isjtobe preferred.

Having now indicated in a general way the pro- 'cedure in accordancewith my invention, I will now proceed to a more detailed descriptionthereof with reference to the following examples.

. Example I One hundred pounds of the paraflln hydrocarbon-insolubleresin derived from pine wood and 5 gallons of China-wood oil are placedin a suitable reaction vessel, such as, for example, a varnish kettle,and the temperature raised to about 480 F.-500 F. at which time 6 poundsof litharge and 4 pound of manganese dioxide are added thereto and thetemperature of the mixture raisedto about 575 F. It is held at thattemperature until foaming subsides and then an additional 15 gallons ofChina-wood oil are added and the temperature is then again raised toabout 565 F. The mixture is held at that temperature until a string fromglass is obtained, a method well known to those skilled in the art. Thetemperature of the reaction mass is'then lowered by adding 5 gallons ofadditional Chinawood .oil and when it has cooled'to a temperaturepreferably of about 450? F.-475 F. it is reduced with 60 gallons of apetroleum naphtha having, for example, a boiling range from about 300 F.

to about 400 F. Any'petroleum type diluent ordinarily used in thevarnish industry can, of course, be used instead. 5

After thinning, as above, a varnish is obtained having anon-volatilecontent of about 43% and I which can be used as such where a varnish isrequired which, when hardened, by air drying, force drying or bakingleaves a film possessing the qualities of toughness, good adhesion andexcellent resistance to water, acids, alkalles and oils. I l I ExampleII .40 The increase in theipetroleum diluent toler- 'ance of paraffinhydrocarbon-insoluble resin derived from pine' wood-oil'vamishes cookedboth with andwithout the metal compounds above mentioned, is-clearlybrought out by the results shown below. Varnisheswere made in accordancewith the procedure, 'heretofore outlined, using various quantities oflinseed' 01- and thinned in each case to a non-volatile content of Forthis work a lead-manganese combination was 50f chosen, consisting 'of 3%lead' and 0.2% manganese on the basis of the oil'present, the lead andmanganese being incorporated, in the manner indicated before in the formof lithargeand manganese dioxide respectively. The results obtainedafter thinning are shown below.

The above data clearly indicate the increased tolerance, for a paramnhydrocarbon type diluent, of a varnish made from linseed oil and. aparaflln hydrocarbon-insoluble resin derived from 75 pine wood, whichcontains a metal combination cooked into the varnish during itsmanufacture,

over a similar varnish cooked in the same way but without any metaIcontent. i

The linseed oil-used in theabove varnishes may be replaced by anyof thedrying or semi-drying 5 oils among which are, for example, China-woodoil, perilla oil, fish oils, soya bean oil as well as the more recentlydeveloped synthetic drying oils.

Similarly, the lead-manganese mixture above 10 shown may be replaced bya different percentage mixture of these metals, or by the single metalsor various mixtures of these, in amounts as previously shown.

Itwill be understood that the examples given 15 herein are by way ofillustration only and that the scope-of my invention is not limitedthereto.

What I claim and desire toprotect by Letters Patent is:

1. The method of making a varnish, contain; 0 ing a paraflinhydrocarbon-insoluble resin dedrived'from pine wood, having asubstantial toldrying oils and a compound of a metal selected from thegroup consisting of zinc, lead, tin, manganese, cobalt, and mixturesthereof, said coinpound being characterized by substantial reac "-tivitywith the oilgresin.mixtureatteniperatures of cooking. I

2. The method or making a var isu co taming a paraflin' hydrocarboninsoluble resiri de- 35 rived from pinewood, having a "substantialtolerance for a paraffin hydrocarbon, liquid'at ordi- Qnarytemperatures, whichfincludes the step of cooking together at ,atemperatu're from about 565 F. to about "60051 forja pe'riddofftlme 40necessaryto give the desired body to .thevarnish,

said resin, a drying'foil and-"a compound of a metal selected from thegroup -consisting of zinc, lead, tin,ma nganese, cobalt'andmixtur'esthereof, ,said compound being characterized by sub- 45 stantial'reactivitywith the oil -resin mixturejati r the temperaturesof'cooking.i 3. The method :of making a varn'ish, containing a paraflin hydrocarboninsoluble resin derived from pine wood, having a substantial tol- 50erance for a'paraflin hydrocarbon, liquid at ordi-. nary temperatures,which includes the step of cooking together at a temperature from about565 F. to about 600 F. for a period of time necessary to give thedesired body to the varnish, said resin, a semi-drying oil and acompound of a metal selected from the group consisting of zinc, lead,tin, manganese, cobalt and mixtures thereof, said compound beingcharacterized by substantial reactivity with the oil-resin mixture atthe temperatures of cooking.

4. The method of making a varnish, containinga paraflinhydrocarbon-insoluble resin derived from pine wood, having a substantialtolerance for a paraflin hydrocarbon, liquid at ordinary temperatures,which includes the step of cooking together at a temperature from abouting a paramn hydrocarbon-insoluble resin derived from pine wood, havinga substantial tolerance for a paraiiin hydrocarbon, liquid at ordinarytemperatures, which includes the step of cooking together at atemperature from about 565 F. to about 600 F. for a period of timenecessary to give the desired body to the varnish, said resin,China-wood oil and a compound of a metal selected from the groupconsisting of zinc, lead, tin, manganese, cobalt and mixtures thereof,said compound being characterized by substantial reactivity with theoil-resin mixture at the temperatures of cooking.

6. The method of, making a varnish, containing a paraflinhydrocarbon-insoluble resin derived from pine wood, having a substantialto1er-' ance for a paraflin hydrocarbon, liquid at ordinarytemperatures, which includes the step of cooking together at atemperature from 565 F. to about 600 F. for a period of time necessaryto give the desired body to the varnish, said resin, soya bean oil and acompound of a metal selected from the group consisting of zinc, lead,tin, manganese, cobalt and mixtures thereof, said compound beingcharacterized by substantial reactivity with the oil-resin mixture atthe temperatures of cooking.

7. The method of making a varnish, containing a paramnhydrocarbon-insoluble resin derived from pine wood, having a substantialtolerance for a paraflin hydrocarbon, liquid at ordinary temperatures,which includes the step of cooking together at a temperature from about565 F. to about 600 F. for a period of time necessary to give thedesired body to the varnish,

said resin, China-wood oil and a mixture of litharge and manganesedioxide such that from about 1% to about 5% lead and from about 0.1%

to about 0.5% manganese, as free metal respectively, of the weight ofsaid oil, are present:

8. The method of making a varnish, containing a paraflinhydrocarbon-insoluble resin derived from pine wood, having a substantialtolerance for a paraffin hydrocarbon, liquid at ordinary temperatures,which includes the step of cooking together at a temperature from about565 F. to about 600 F. for a period of time necessary to give thedesired body to the varnish, said resin, soya bean oil and a mixture oflitharge and manganese dioxide such that from about 1% to about 5% leadand from about 0.1% to about 0.5% manganese, as free metal respectively,of the weight of said oil, are present.

9. The method of making a varnish, containing a paraflinhydrocarbon-insoluble resin derived fjrom pine wood, having asubstantial tolerance for a paraffin hydrocarbon, liquid at ordinarytemperatures, which includes the step of cooking together at atemperature from about 565 F. to about 600 F. for a period of timenecessary to give the desired body to the varnish, said a resin, an oilselected from the group consisting of drying oils and semi-drying oilsand an amount of a zinc compound, reactive with the oil-resin mixture atcooking temperatures, such that from about 0.5% to about 1% zinc, asfree metal, on the basis of the oil, is present.

10. The method of making a varnish, containing a paraflinhydrocarbon-insoluble resin derived from pine wood, having a substantialtolerance for a paraiiln hydrocarbon, liquid at ordinary temperatures,which includes the step of cooking together at a temperature from about5. The method of making a varnish, contain- 565 F. to about 600 F. for aperiod of time necessary to give the desired body to the varnish, saidresin, an 011 selected from the group consisting of drying oils andsemiedrying oils and an amount of a manganese compound, reactive withthe oil-resin mixture at cooking temperatures, such that from about 0.4%to about 0.8% manganese, as free metal, on the basis of the oil, ispresent.

11. The method of making a varnish, containing. a paraifinhydrocarbon-insoluble resin derived from pine wood, having a substantialtoler- 'ance for a paraflin hydrocarbon, liquid at ordinarytemperatures, which includes the step of cooking together at atemperature from about 565 F. to about 600 F. for a period of timenecessary to give the desired body to the varnish, said resin, an oilselected from the group consisting of drying oils and semi-drying oilsand a mixture of a lead compound and a manganese compound, reactive withthe oil-resin mixture at cooking temperatures, such that from about 1%to about 5% lead and from about 0.1% to about 0.5% manganese, as freemetal respectively, of the weight of oil, are present.

12.- A varnish comprising a paramn hydrocarbon which is liquid atordinary temperatures and the product obtained by reacting asubstantially paraflin hydrocarbon-insoluble resin derived from pinewood, an 011 selected from the group consisting of drying oils andsemi-drying oils and a compound of a metal selected from the groupconsisting of zinc, lead, tin, manganese, cobalt and mixtures thereof,by the process specified in claim 1.

13. A varnish comprising a paraflln hydrocarbon which is liquid atordinary temperatures and the product obtained by reacting asubstantially paraflin hydrocarbon-insoluble resin derived from pinewood, an oil selected from the group consisting of drying oils andsemi-drying oils and a compound of a metal selected from the groupconsisting of zinc, lead, tin, manganese,

- cobalt and mixtures thereof by the process'speci- "the productobtained by reacting a substantially paraflin hydrocarbon-insolubleresin derived from pine wood, an oil selected from the group consistingof drying oils and semi-drying oils. and a compound of zinc by theprocess and in the amounts specified in claim 9.

15. A varnish comprising a pa'raflin hydrocarbon which is liquid atordinary temperatures and the product obtained by reacting asubstantially paraflin hydrocarbon-insoluble resin. derived from pinewood, an oil selected from the group consisting of drying oils andsemi-drying oils and a manganese, compound by the process and in theamounts specified in claim 10.

16. A varnish comprising a paraflin hydrocarbon which is liquid atordinary temperatures and the product obtained by reacting asubstantially paraffin hydrocarbon-insolubleresin derived from pinewood, an oil'selected from the group consisting of drying oils andsemi-drying oils and a mixture of a lead compound and a manganesecompound by the process and in the amounts specified in claim 11.

EVART E. MAYFIELD.

